Dihydroxy polyaromatic ether



United States Patent 3,287,421 DIHYDROXY POLYAROMATIC ETHER Daniel W.Fox, Pittsfield, Mass, assignor to General Electric Company, acorporation of New York No Drawing. Original application July 19, 1956,Ser.

No. 598,768, now Patent No. 3,148,172, dated Sept. 8,

1964. Divided and this application Sept. 26, 1963, Ser.

1 Claim. (Cl. 260-613) This is a division of application Serial No.598,768 filed July 19, 1956, now US. Patent 3,148,172.

This invention relates to aromatic carbonate resins, aromatic ethersuseful in preparing said resins, and to methods of preparing said resinsand ethers. More particularly, this invention relates to a carbonateresin characterized by alternating carbonate groups and ether-containingorganic groups bonded to each other; each ethercontaining organic grouphaving at least two aromatic carbocyclic radicals bonded to each otherby means of an ether linkage; each carbonate group being bonded directlyto a nuclear carbon of one aromatic radical of each ether-containingorganic group. Still more particularly, this invention relates to alinear polymer characterized by recurring structural units of theformula where A is the residue of an aromatic nucleus; Y is an organicor an inorganic radical, for example, monovalent hydrocarbon,halogenated monovalent hydrocarbon, organoxy such as alkoxy, etc.,halogen, nitro, etc., m is a whole number equal to from to a maximumdetermined by the number of replaceable nuclear hydrogens substituted onthe aromatic hydrocarbon residue A; and q is a whole number equal to atleast 1.

Many carbonate resins are known. Among these carbonate resins are thoseprepared by the vinyl polymerization of unsaturated carbonate esterssuch as alkyl carbonates, etc., those resins prepared from the esterinterchange of carbonate esters with aliphatic glycols and those resinsprepared by reacting dihydroxy monoaryl compounds, such as hydroquinoneand resorcinol, with carbonate precursors, such as phosgene or carbonateesters. Although these known carbonates have found some uses asmodifiers, plasticizers, hydraulic fluids, etc., they have neverachieved industrial importance as individual thermoplastic entitiesbecause of their poor properties, for example, they are too low melting,too insoluble, too unstable, etc.

I have now discovered that carbonate resins within the scope of FormulaI can be readily prepared and have excellent physical, chemical,electrical, thermal, etc. properties.

In general, the carbonate resins of this invention can be prepared byreacting a dihydroxyaromatic ether with any suitable carbonateprecursor. The dihydroxy aromatic ether is characterized by two terminalhydroxy groups bonded to an ether-containing organic group, saidether-containing organic group having at least two aromatic carbocyclicradicals bonded to each other by means of an ether linkage, and saidterminal hyd-roxy groups being bonded directly to a nuclear carbon ofthe first and last aromatic radicals. Where the dihydroxyaromatic etherhas at least three aromatic carbocyclic radicals bonded to each other bymeans of an ether linkage, the compound is called a dihydroxypolyaromatic ether.

One method of preparing these resins comprises effect ing reactionbetween (1) a dihydroxy aromatic ether, for example of the formula (II)(Y)m (Y)m gL l a L J. also referred to as a dihydroxyether and (2) adiaryl carbonate, for example of the formula Where A is the residue ofan aromatic nucleus; Y and Z are inorganic or organic radicals, saidradicals being inert to and unaflected by the reactants and by thereaction of the dihydroxyether and the diaryl carbonate; m and n areWhole numbers equal to from 0 to a maximum equivalent to the number ofreplaceable nuclear hydrogens substituted on the aromatic hydrocarbonresidue A; and q is a whole number equal to at least one.

In the above formula for the dihydroxyether, the inert substituentsdesignated by Y on each aromatic hydrocarbon residue may be the same ordifferent; the number of Ys on each respective aromatic hydrocarbonnucleus residue A may also be varied if desired so that a symmetrical oran unsymmetrical compound be formed. The Zs in the diaryl carbonatedefined by Formula 111 may also be the same or different, and the numberof substituents represented -by Z may be the same on each aromaticnucleus A, or may vary depending upon the degree of substitution desiredon each aromatic residue A.

Among the inert substituents which Y and Z may represent are, forinstance, halogens (e.g., chlorine, bromine, fluorine, etc); organoxyradicals of the formula OR, Where R is a monovalent hydrocarbon radical;and monovalent hydrocarbon radicals of the type represented by R. Otherinert substituents included within the scope of Y and Z, such as thenitro group, may be substituted on the aromatic nuclear residue Awithout departing from the scope of the invention.

Among the monovalent hydrocarbon radicals which R may represent are, forinstance, alkyl radicals (e.g. methyl, ethyl, propyl, isopropyl, butyl,decyl, et-c.), aryl radicals (e.g., phenyl, naphthyl, biphenyl, tolyl,xylyl, ethylphenyl, etcj), aralkyl radicals (e.g. benzyl, phenylethyl,etc), cycloaliphatic radicals (e.g., cyclopentyl, cyclohexyl, etc), aswell as monovalent hydrocarbon radicals containing inert substituentsthereon, for in- HO OH stance, halogens (e.g., chlorine, bromine,fluorine, etc.).' Among the aromatic nuclei which A may represent are,

for instance, the aromatic hydrocarbon residues based on benzene,biphenyl, naphthalene, anthracene, etc. The final configuration of thisaromatic hydrocarbon residue in the molecule is determined by thenuclearly-substituted hydroxyl groups, together with anynuclearly-substituted hydrogen atoms and the number of inertsubstituents represented by either Y or Z.

In the above formulae, m and n may be zero whereby the aromatic nuclearresidues A will be unsubstituted except for the hydroxyl groups inregard to Formula II, or else there may be a plurality of substitutionsof inert substituents on the aromatic nuclear residues depending uponthe number of nuclearly bonded hydrogens remaining on A, taking intoconsideration the presence of the hydroxyl groups in'Formula II. Where qis equal to one, the compound of Formula II is a monoether. When q isgreater than one, this compound is a polyether.

The posit-ions of the hydroxyl groups Y and Z on the aromatic nuclearresidue A, may be varied in the ortho, mema or para positions, and thegroupings may be in a vi-cinal, asymmetrical, ior symmetricalrelationship, Where two or more of the nuclearly-bonded hydrogens of the3 aromatic hydrocarbon residue are substituted with, for instance Y, andthe hydroxyl group in Formula II.

In general, the aromatic carbonate resins of the instant invention canbe prepared by interaction between the reactants at elevatedtemperatures of trom about 150 C. to 300 C. or higher tor times varyingfrom about 1 to 15 or more hours under such conditions that an esterinterchange occurs whereby, concurrently with the heating, there isremoved from the reaction mixture a composition having the formula whereA, Z and n have the meanings given above. This ester interchangeevolution of the hydroxyaryl compound (represented by Formula 1V)advantageously carried out at sub-atmospheric pressure, for instance, atreduced pressures of around 0.01 to 5 to mm. of mercury, preferablywhile .blauketing the reaction mixture with a nonoxidizing or an inertatmosphere, such as hydrogen or nitrogen, neon, krypton, etc, to preventundesirable oxid'a-tive effects especially under such conditions whereextremely high reaction temperatures are employed under moderatesub-atmospheric pressures. The use of atmospheric (and superatmosphericpressures is, however, not precluded. Heating under vacuum after theester exchange is substantially completed (hereaztter called vacuumcooking"), for example .at from 150300 C. at 0.01 to 5-10 mm. forextended periods of time, tends to increase the molecular weight andviscosity of the carbonate resin.

Although the reaction can be carried out in the absence of a catalyst,one may, if desired, use the usual ester exchange catalysts, forinstance, metallic potassium, calcium, beryllium, magnesium, zinc, cad-.mium, aluminum, chromium, molybdenum, iron, cobalt, nickel, chromium,silver, gold, tin, antimony, lead, bariurn, strontium, platinum,palladium, etc, compounds thereof, such as alcoholates, oxides,carbonates, acetates, hydrides, etc. Additional catalysts and variationsin the ester interchange methods are discussed in Groggins, UnitProcesses in Organic Synthesis (4th Ed., McGraW-Hill Book 00., 1952),pages 616-620. The amount of such catalyst is usually quite small and isof the order of 0.001 to 0.1%, or more, by weight, based on the totalweight of the reactants.

Although equimol-ar ratios of the diaryl carbonate and thedihydroxyether or excesses of either reactant can be used to make theresinous compositions of the instant invention, an excess (based onmolecular equivalents,

hereafter called molar excess) of the diaryl carbonate is preferredsince products of higher molecular weights and viscosities can be moreeasily obtained with excess diaryl carbonates. Thus, I have employed thediary] carbonate and the dihydroxyether in essentially molar equivalentsor in molar concentrations which are almost equal using for each mole ofthe dihydroxyether from about 0.98 to about 1.02 moles of the diarylcarbonate, or larger molar excesses of the diaryl carbonate, forinstance, by employing, for each mole of the dihydroxyether, from about1.05 to 2.0 moles or more of the diaryl carbonate. Molar excesses of thedihydroxyether can also be employed, particularly when thedihydroxyether is more volatile than the diaryl carbonate.

Although I prefer to carry out the ester interchange with diarylcarbonates, other carbonate esters can also be employed. These othercarbonate esters comprise dialkyl esters (wherein the alkyl radicals arefor example, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, decyl,octadecyl, etc.) dicycloailkyl esters comprising for example,cyclopentyl, cyclohexyl, cycloheptyl, etc, and the like.

The carbonate resins can also'be prepared by introducing p'hosgene intosolutions of dihydroxyethers (in organic solvents, for example organicbases, such as ter- 4 tiary amines (e.-g. pyridine, dimethylaniliue,quincline, etc). The organic bases can be undiluted or diluted withinert solvent, tor example hydrocarbons, such as benzene, toluene,xylene, etc, halocarbons, such as chloreform, etc. The advantage oftertiary airlines is that vthey are unreactive, are good solvents andact as acid acceptors for HCl given off during the react-ion. Althoughthe phosgene reaction can be carried out over a wide temperature range,such as below 0' C. to C. or higher, the reaction proceedssatisfiactorily at 25 C. to 50 C. Since the reaction is exothermic, therate of phosgene addition can be used to control the temperature of thereaction. I have found that the ratio of phosgene to dihydroxyether canbe varied over wide limits. Substand-ally equimolar amounts can be used,although an excess of from 1.05-1.5 moles or more of phosgene ispreferred. The concentration of dihydroxye-ther in solvent oan also bevaried within wide although for ease of reaction and handling I preferto use a solution containing from 5 to 50% by weight of dihydroxyether.

In general the p hosgene reaction is carried out by dissolvingdihydroxye-ther in an organic base, such as pyridine. The system isthenflushed with nitrogen and the temperature of the reaction mixture isadiusted by heating or cooling, if desired, and phosgene is passed intothe mixture at the desired rate. After the reaction is com pleted, thepolymer is precipitated by any suitable means; tor example, by pouringthe reaction product into a wellstirred liquid capable of effectingprecipitation, for example, hydrocarbons, alcohols, etc. Anhydrousprecipitants are preferred but water may also be used. After filtrationthe precipitate is washed with methanol or other solvent capable ofremoving pyridine and pyridine hydrochloride to yield upon drying afine-1y divided fibrous product.

Another method of preparing aromatic carbonate resins comprises reactingphosgene with aqueous solutions of soluble salts (for example, sodium,potassium, etc. salts) of the dihydroxyether whereby carbonate resinseparates generally as a fibrous curd from aqueous solution due to itsinsolubility. Where low molecular weights are produced by this aqueousprocess, the product can be neutralized, washed with water and furtherreacted with diary l carbonate to a higher molecular weight. A productof higher molecular weight can be obtained [from the aqueous procemwithout treatment with diaryl carbonate by adding solvents to the wateror by forming aqueous organic emulsions which elfect greater solubilityof the phosgene and keep the carbonate resin in solution until a highermolecular weight is obtained. The product so formed is washed with acid,such as hydrochloric acid to neutralize the product. The productproduced in this manner can be used as a molding powder, or dissolved insolvents to produce useful as surface coatings. As a result of thesereactions there is obtained a linear polymer comprising structural units'of the tormula (V Y m Y m 0 l0lalt t L J. 1 where A, Y, m, and q havethe meanings given above. During the course of the reaction x is a wholenumber equal to at least 1 and may grow to as high as 500 or more. Theseproducts are useful thermoplastic resinous materials which have goodthermal resistance, high heat distortion temperature, extremely highmechanical strength, and excellent electrical characteristics, etc.

Some of the dihydroxyethers useful in preparing carbonate resins areknown while others are disclosed herein for the first time. An excellentsummary of methods of preparing dihydroxyethers is found in ChemicalReviews 38, 414 117 (1946).

One method of preparing dihydroxyether is the Ullrnan reaction wherein ahalogenated phenol such as p-brornopowder. To be assured of terminalhydroxy groups on the dihydroxyether it is advantageous to have at leastone phenol group on each phenolic compound etherified prior to reaction.Upon completion of the reaction these terminal etherified groups areremoved by any suitable means such as by treatment with a hydrogenhalide, for example HI, HBr, etc.; treatment with a solvent containingaluminum halide, such as AlCl AlBr etc. Acetic anhydride or other acidanhydrides can be added to the aqueous halogen acids to effectivelyremove some of the water, raise the boiling points, improve solubility,etc. Since methyl ethers give high yields and since they can be readilydemethylated, they are generally used. Etherification is affected bysuch common etherifying agents as dimethylsulfate, etc.

Of course, other methods of preparing dihydroxyethers can also beemployed, for instance, the method disclosed in U.S. Patent 2,739,171,Linn, wherein dihydroxyaromatic compounds, such as hydroquinone,resorcinol, catechol, dihydroxynaphthalene, etc. are dehydrated withsuitable agents to dihydroxy ethers; the hydrolysis of dihaloaromaticcompounds, etc.

By modifying the above Ullman-type reaction, dihydroxypolyphenyletherscan be prepared. Thus, by substituting a dihalo aromatic compound, suchas dihalobenzene, dihalodiphenylether, dihalodiphenyl, etc. for thealkoxy halo aromatic compound, such as bromoanisole, there is obtaineddimethylethers of the corresponding dihydroxypolyaromatic ethers. Thesemethylated compounds can be demethylated to the correspondingdihydroxyether. By varying the ratio of dihaloarornatic compounds toalkoxyphenate and by repeating the reaction with the intermediatesformed in a prior step, there is obtained dihydroxy polyethers ofvarying molecular weights.

These dihydroxy polyaromatic ethers are shown in Formula II wherein q isa whole number having a value of from 2 to or higher.

In order that those skilled in the art may better understand how thepresent invention may be practiced, the following examples are given byway of illustration and not by way of limitation. All parts are byweight unless otherwise stated.

Example 1 The example illustrates the preparation ofp,p'-dimethoxydiphenylether. One mole of p-bromoanisole, two moles ofp-methoxyphenol, 1 mole of potassium hydroxide and 10 grams of copperpowder are placed in a reactor equipped with a stirrer, a thermometerand a reflux condenser fitted with a trap which allows the removal ofwater. The reactor is heated to 240 C. over one hour, vigorous stirringbeing accomplished by using a ball of copper wool as a stirring blade.During the first hour most of the water formed from the reaction ofp-methoxyphenol and potassium hydroxide is removed by distillation. Thereaction is then continued for about 4 more hours at 240 C.

After the reaction is completed, the reaction mass is cooled to about200 C and poured into a 5% aqueous solution of KOH. The organic residuecomprising p,pdimethoxydiphenylether is washed repeatedly andalternately with 5% aqueous KOH and water. The crude product is dried,then distilled and the fraction boiling at 340 C. (atmospheric pressure)is collected.

The distilled product, p,p-dimethoxydiphenylether, has a melting pointof 103 C.

Example 2 This example illustrates the preparation ofp,p'-dihydroxydiphenylether. The demethylation ofp,p'-dimethoxydiphenylether is accomplished by refluxing for eight hours50 grams of the product prepared in Example 1 in a mixture of 250 gramsof acetic anhydride and 250 grams of 48% hydrobromic acid. Thedemethylated mixture was then added to about 2 liters' of ice and watercausing precipitation of the product. This precipitate is collected,dissolved in 5% aqueous KOH, filtered and reprecipitated by neutralizingwith concentrated hydrochloric acid. The crude precipitate is thenpurified by first dissolving in a minimum of acetone and thenprecipitating by adding the acetone solution to boiling toluene. Theproduct, p,pdihydroxydiphenylether, has a melting point of 164.5 C.

Example 3 This example illustrates the preparation ofp,p'-dimethoxytriphenylether The reaction is carried out in the mannerof Example 1 except that p-dibromobenzene is used in place ofp-bromoanisole. The ingredients employed in the reaction are 3 moles ofp-methoxyphenol, 1 mole of p-dibromobenzene and 2 moles of KOH. As inExample 1 the total reaction time is 5 hours.

The product is purified by cooling to about 200 C., and pouring into a5% aqueous solution of KOH and repeatedly and alternately Washing with5% aqueous KOH and water. The crude product resulting from thistreatment is further purified by dissolving in chlorobenzene and passingthe solution through a column of Magnesol (magnesium silicate).p,p'-Dimethoxytriphenylether is precipitated by pouring thechlorobenzene solution into petroleum ether to yield a product having amelting point of 144-145 C.

Example 4 This example illustrates the preparation ofp,p'-dihydroxytriphenylether (VII) fio g yamapa Attempts to demethylatep,p'-dimethoxytriphenylether by the method described in Example 2 or byHI-HBr mixture are unsuccessful without the use of pressure, probablydue to low solubility of the triphenylether. However, the followingprocedure is satisfactory.

p,p-Dimethoxytriphenylether (25 grams), 75 grams of anhydrous aluminumchloride and 300 ml. of benzene are placed in a reactor equipped with areflux condenser and refluxed for two hours. The product is isolated byadding water, steam distilling ofI benzene and filtering. The crudeproduct is dissolved in 5% aqueous KOH and filtered. The desiredcompound in the filtrate is precipitated by neutralizing withhydrochloric acid. This precipitate is filtered, dried and purified byseveral recrystallizations from benzene, ethyl acetate and petroleumether. The product, p,p-dihydroxytriphenylether, has a melting point of196 C.

Example 5 This example illustrates the preparation ofbisp-methoxyphenylether) -4,4'-biphenyl, (VIII) which is prepared by themethod of Example 3 except that p,p-dibr0mobiphenyl is substituted forp,p'-dibromobenzone. The product is decolorized by dissolving in hotchlorobenzene and filtering through a Magnesol column. The purifiedproduct (Formula VIII) which separated on cooling has a melting point of210-212 C Example 6 This example illustrates the preparation ofbis-(p-hydroxyphenlyether)-4,4'-biphenyl which is prepared bydemethylating the product of Example 5 by the process described inExample 4. The demethylated product is dissolved in 5% KOH, filtered,and reprecipitated by neutralizing with hydrochloric acid. Theprecipitate, filtered, dried, and purified by several recrystallizationsfrom ethyl acetate and petroleum ether, has a melting point of 241-243C. and is the demethylated product of the compound of Formula VIII.

Example 7 This example illustrates the preparation by the esterinterchange method of a resin having recurring units of the formulap,p'-Dihydroxydiphenylether (1 mole) and diphenyl carbonate (2 moles)275 -300 C. excess diphenyl carbonate is distilled over.

When the ester interchange is substantially complete, the product isvacuum cooked for 6 additional hours at 300 C. at -10 mm. pressurefollowed by 4 hours additional heating to 375 C. under the samepressure. A near quantitative yield is obtained. A cold rod is insertedin the hot melt and a fiber pulled out. It is tough and is very readilycold drawn.

This product (Formula D0, which is a crystalline material, is pressedinto 15 mil sheets. It has a dielectric strength at 27 C. (short time,about 40 seconds, breakdown) of 30 kilovolts or 2000 volts/mil, and atensile strength of 6000 p.s.i.

This product can also be cast into film from dioxane solution. Thecrystalline film becomes amorphous at 225-235 C.

Example 8 This example illustrates the preparation by ester interchangeof a resin having recurring units of the formula O O O O E Example 9This example illustrates the preparation of a resin having the repeatingunits shown in Formula IX by the phosgene-pyridine method.

One part of p,p'-dihydroxydiphenylether is dissolved in 10 parts ofanhydrous pyridine contained in a reactor equipped with a stirrer, athermometer, and a gas inlet and outlet tube. After the flash is flushedwith nitrogen, phosgene gas is admitted below the surface of thesolution at such a rate that the temperature of the reaction is keptbelow 30 C. without external cooling. After about 25 minutes there is avery pronounced increase in viscosity. During this period, slightly morethan an equimolar ratio of phosgene is added (about a 10% excess ofphosgene based on p,p-dihydroxydiphenylether). The polymer is thenprecipitated by pouring the reaction mixture into well-agitatedn-hexane. The polymer slurry is filtered, poured again into toWell-agitated n-hexane and washed with well-agitated anhydrous methanol.The resulting 8 polymer (Formula IX) after being dried overnight at C.is white, and can be cold drawn from a melt.

Example 10 This example illustrates the preparation of a resin havingthe repeating units shown in Formula XI by the phosgene-pyridine method.

One part of p,p'-dihydroxytriphenylether is dissolved in 20 parts ofanhydrous pyridine and reacted and purified in the manner of Example 8.The purified polymer (Formula XI) is similar in appearance to thatobtained from p,p-dihydroxydiphenylether.

Example 11 This example illustrates the preparation of a resin havingrecurring units of the formula (XII) HBr -o- 0H (AehO (alkyl) 11:(alkyl) 51 (XIII) Example 12 One mole of o-methyl-p-bromoanisole, 2moles of omethyl-p-methoxy phenol, 1 mole of KOH, and 10 grams of copperpowder are reacted and demethylated according to the methods of Examples1 and 2 to produce O -OH One mole of this compound is then reacted with2.0 moles of diphenyl carbonate according to the method of EX- ample 7to prepare a carbonate resin having recurring units of the formula (XV)O This product can also be prepared by the phosgene-pyridine method ofExample 8.

The presence of ortho groups (relative to the hydroxy group) on thedihydroxyether moiety of the carbonate resin imparts high alkalinestability to the final product. For example, a molded piece of the aboveproduct can be boiled with aqueous alkaline for long periods of timewithout degradation. These ortho substituted resins also exhibit highhydrolytic stability, for example, a portion of this same resin issealed in a tube with Water and heated at C. for several days with noapparent degradation.

Halogen derivatives are prepared by halogenating dimethoxydiphenylethers according to the method described in Lions et al., 1.Proc. Roy. Soc., N.S. Wales 72, 257 (1939).

Example 13 One mole of p,p-dimethoxydiphenylether is halogenatedaccording to Lions method to yield a mixture of chlorinated products.This product is demethylated according to the process of Example 2 toyield (XVI) (Cl-)m (Cl)m In addition to the specific reactants describedabove in the ester interchange method, other diaryl carbonates anddihydroxyethers can be employed. Examples of other carbonate esterscomprise symmetrical carbonates, for example di-(halophenyl) carbonatese.g. di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate;di-(polyhalophenyl) carbonates e.g. di-(trichlorophenyl) carbonate,di-(tribrornophenyl) carbonate, etc.; di-(alkylphenyl) carbonates e.g.di-(toly-l) carbonate, etc., di-(naphthyl) carbonate,di-(chloronaphthyl) carbonate, etc.; unsymmetrical carbonates, forexample, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate,trichlorophenyl chlorotolyl carbonate, etc. Mixtures of the foregoingcarbonate esters can also be employed.

These diaryl carbonates can be prepared by the methods described in A.F. Holliman et al., Rec. Trav. Chem. 36, 271 (1916), and Copisarow, J.Chem. Soc. (Brit), 1929, 251, both of whom discloses preparing dicresylcarbonate by treating the alkali metal salts of p-cresol with phosgene,and US. Patent 2,362,865Tryon et al. which discloses preparing diphenyl,ditolyl, and dinaphthyl carbonates by passing phosgene through a columnof the phenol in the presence of a catalyst, etc.

Examples of other dihydroxy ethers comprise the 4,3'-, 4,2-, 4,1'-,2,2'-, 2,3'-, etc. dihydroxy diphenyl ethers;4,4'-dihydroxy-2,6-dimethyl-diphenylether; 4,4-dihydroxy-2,5-dimethyl-diphenyl ether; 4,4-dihydroxy-3,3-di-isobutyl-diphenylether; 4,4'-dihydroxy-3,3'-diphenyl ether; 4,4-dihydroxy-3,3-diisopropyldiphenyl ether; 4,4-dihydroxy-3,2-dinitro-diphenyl ether;4,4-dihydroxy-3,3'-dichloro-diphenyl ether; 4,4'-dihydroxy-3,3'-difluorodiphenyl ether; 4,4-dihydroxy-2,3'-dibromo diphenyl ether; 4,4-dihydroxydinaphthyl ether; 4,4'-dihydroxy 3,3'-dichlorodinaphthyl ether;2,4-dihydroxy-tetraphenyl ether; 4,4-dihydr-oxy-pentaphenyl ether;4,4'-dihydroxy-2,6-dimethoxy-diphenyl ether;4,4-dihydroxy-2,5-diethoxydiphenyl ether, etc.

Mixtures of these dihydroxyethers can also be employed. Because of theirexcellent physical, mechanical, chemical, electrical and thermalproperties the products of this invention have many and varied uses. Forexample, they can be used in molding powder formulations, either alone,or by mixing them with various fillers such as wood flour, diatomaceousearth, carbon black, silica, etc. to make molded parts such as spur,helical, worm or bevel gears, ratchets, bearings, cams, impact parts,gaskets, valve seats for high pressure oil and gas systems or otherchemical fluids requiring resistance to chemicals, etc.

Films of these products prepared by calendering or extrusion (eitherorientated or not) are useful as metal or fiber liners, containers,covers, closures, electrical insulating tapes, in sound recording tapes,pipe coverings, etc. Because of their chemical inertness, tubing ofthese materials can be used to transport chemicals, such as acids andbases, which might be deleterious to other resins. Because of theirchemical, physical and thermal properties, they may be used as surfacecoating for such apparatus as refrigerators, washing machines, cookingovens, etc. Additional uses are as rods, wire coating, wire enamels,slot insulations in dynamoelectric machines, fibers, etc. These resinscan also be employed in varnish and paint formulations and as bondingmaterial for metallic or fibrous laminates. The carbonate resins of thepresent invention may be mixed with various fillers, modifying agents,etc. such as dyes, pigments, stabilizers, plasticizers, etc,

Copolymers of dihydroxyethers are also included within the scope of thisinvention, e.g. carbonate resins wherein a plurality of dihydroxyethermoieties are contained within the same carbonate resin, such as theproduct formed from the simultaneous reaction of mixtures of a pluralityof dihydroxyethers with a diaryl carbonate or phosgene, etc.; forexample, the carbonate resins formed by reacting a mixture ofunsubstituted dihydroxyether or corresponding polyethers and alkyldihydroxyether or corresponding polyethers with diphenyl carbonate orphosgene or the carbonate resins formed by reacting mixtures of otherdihydroxyethers.

The foregoing detailed description has been given for clearness ofunderstanding only and no unnecessary limitations are to be understoodtherefrom. The invention is not limited to the exact details shown anddescribed for obvious modifications will occur to those skilled in theart.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

References Cited by the Examiner UNITED STATES PATENTS 2,739,171 3/1956Linn 260-613 LEON ZITVER, Primary Examiner. B. HELFIN, AssistantExaminer.

